Method for treating textile with perfluoroalkyl compounds and the treated textile



United States Patent M 3,232,790 METHOD FOR TREATING TEXTILE WITH PER- FLUOROALKYL CGMPOUNDS AND THE TREATED TEXTILE Heinz Enders, Stadtbergen, near Augsburg, Hans Karl Wiest, Gersthofen, Hans Deiner and Irmgard Christine Munzenmaier, Augsburg, and Josef Brockmeier, Rheydt, Germany, assignors to Chemische Fabrilr Pfersee G.m.b.H., Augsburg, Germany, a firm No Drawing. Filed Aug. 8, 1961, Ser. No. 129,953 6 Claims. (Cl. 117-1395) This invention relates to textile finishing methods, and more particularly to a method of making textiles oil and water repellent.

It is known to treat textiles and other fibrous materials with aqueous solutions or dispersions of compounds which contain a plurality of perfluoroalkyl radicals having at least 4 carbon atoms in each alkyl radical in order to make them oil repellent. The oil repellency produced in this manner does not satisfactorily resist laundering of the textile materials at relatively high temperatures. The

known treatments provide a measure of water repellency, but such water repellency does not meet commercial requirements. It is an added disadvantageof the aforedescribed treating method that aqueous solutions or dispersions of the perfluoroalkyl compounds tend to form coatings on the rolls of a padding machine or the like during treatment of the textiles, and thus render continuous operation of the machines difii-cult, or even impossible.

It is the primary object of the invention to provide a treatment for making textile materials oil and water repellent which avoids the drawbacks of the known method described above while retaining its well known advantages.

A more specific object of the invention is the provision of a method for treating textile materials with perfluoro- .alkyl compounds of the type described to obtain a finish which resists laundering at relatively high temperatures.

Another object is the provision of such a method which can be continuously carried out on conventional equipment of the padding machine type without requiring interruption of the process because of the formation of coatings on the machine rolls.

An additional object of the invention is the provision of a finishing method which provides a good, soft hand to the material treated. A further obiect is the provision of a method which is well suited for the treatment of syntheticfiber materials.

Yet another object is the provision of a textile finishing "method which is applicable to cotton and rayon fabrics,

and may be employed on such fabrics in conjunction with conventional procedures for making the fabrics wrinkle resistant.

We have found that the shortcomings inherent in known textile treating methods employing perfluoroalkyl compounds can be overcome by adding to the treating bath dispersions of an N-alkyl-N',N'-alkylene urea the alkyl radical of which has more than 10, and preferably 11 to 22 carbon atoms, and the alkylene radicals of which have 2 to 3 carbon atoms.

Quite surprisingly it has been found that even very small amounts of these alkyl-alkylene ureas not only 3,232,790 Patented Feb. 1, 1966 greatly improve the water repellency eifects of the treating bath, but that they also completely prevent the formation of coatings on the rolls of the padding machines during the treatment of the textile materials. Extended continuous runs are possible. Moreover, the oil repellency of the treated fabrics is not only not reduced but the laundry resistance of the water repellent finish is greatly increased.

It is an additional advantage of the method according to the invention that the alkyl-alkylene ureas of the invention impart to the textile material a pleasant, soft hand and agreeable drape.

The method of the invention is particularly well suited for the treatment of woolens and of materials consisting partly or entirely of synthetic fibers, such as polyester fibers, nylons, polyacrylonitrile. Very good effects are also produced on other fabrics of fibrous materials of natural or synthetic origin. It is particularly advantageous to combine the treatment according to the invention with the conventional wrinkle proofing treatment of cellulosic fiber materials such as native cotton or rayon. For this purpose, the fibrous materials aretreated with a finishing solution which, in addition to finishing agents of the invention, contains a suitable synthetic resin forming agent, such as methylol urea, or its ethers,;methylol melamine or its ethers, or reactive resins such as methyl olethylene urea, methyloltriazone derivatives, and the catalysts which are necessary for curing the precondensates jointly employed with these resins. Suitable catalysts include the ammonium salts of strong inorganic acids, which may be used jointly with ammonium salts of weak acids if so desired and salts of multivalent metals such as magnesium, zinc, and the like with strong inorganic acids.

Examples of suitable compounds containing a plurality of perfluoroalkyl radicals each radical having at least 4 carbon atoms include the water soluble chromium coordination complexes of saturated perfluoro-monocarboxylic acids or substituted carboxylic acids having at least one perfiuoro radical with at least 4 carbon atoms as disclosed in US. Patent No. 2,662,835; aqueous dispersions of basic salts of aluminum with perfluoro-monocarboxylic alkanoic acids or substituted carboxylic acids having at least one perfiuoro alkyl radical of at least 4 carbon atoms; aqueous dispersions of polymers or copolymers of esters of 1,l-dihydro-perfluoroalkanols with acrylic acid as disclosed in U.S. Patent. No. 2,642,416; aqueous dispersions of polymers or copolymers, the monomer units having the formula:

wherein R is a perfiuoroalkyl radical having at least 4 carbon atoms; R, is hydrogen .or an alkyl radicalhaving 1 to 6 carbon atoms; R is a divalent alkylene radical having 1 to 12 carbon atoms, and Z is the residue of acrylic or methacrylic acid; or aqueous dispersions of polymers or op lymers, t e mon me un t ving the formula mamma y-R 000};

wherein RF, R1 n R r p e t t e m r c s s mentioned above, and X is a polymerizable radical selected from the group consisting of allyl, methallyl, and vinyl radicals.

Among the N-alkyl-N',N-alkylene ureas having an alkyl radical of more than 10, and preferably 11 to 22 carbon atoms, it is preferred to employ those having an alkyl radical of 15 to 19 carbon atoms. The dispersions of these compounds are prepared in a basically known manner by reacting an aliphatic isocyanatc having a carbon chain of preferably 11 to 22 carbon atoms with an alkylene imine, the alkylene radical of which has 2 to 3 carbon atoms.

The dispersions may be stabilized by the addition of non-volatile, strongly basic compounds, or of volatile bases in conjunction with quaternary nitrogen compounds of the formula wherein R,, is an alkyl radical having more than 10 carbon atoms, R is a pyridin, or oxyethylmorpholine radical, and Z is the residue of a monobasic acid.

The N-alkyl-NQN alkylene ureas .are added to the textile treating baths according to the invention in preferred amounts of 1 to 15 grams per liter.

The amount of the compounds which contain a plurality of perfluoroalkyl radicals is preferably 2 to 15 grams, and more specifically 6 to 10 grams per liter,

The textile material is impregnated, and preferably saturated with the treating baths of the invention which is facilitated by the addition to the baths of a monohydric alkanol having 3 to 4 carbon atoms, or of mixtures of such alcohols. The fibrous material is extracted after impregnation to a desired pick-up, dried at temperatures between 100 and 120 C., and finally cured at temperatures between 130 and 160 C. for periods of 10 to 3 minutes. If synthetic resins and the corresponding curing catalysts are jointly employed with the textile treating agents of the invention, it may be desirable to wash the fibrous material after curing in order to remove residual catalysts.

For the highest oil and water repellency, for a finish which permanently resists laundering and dry cleaning, and for best operating characteristics on the padding machine, that is, for complete avoidance of the formation of coatings on the padding machine rolls, we prefer additionally to mix with the treating solutions certain water insoluble precondensat'es which are soluble in monocarboxylic lower alkanoic acids. These products are obtained by condensing an aminotriazine having at least 2 amino radicals on each triazine ring with formaldehyde and a monohydric alkanol having 1 to carbon atoms. The precondensate contains for each triazine ring at least 1 aliphatic radical having more than 10, and preferably 11 to 22 carbon atoms, and at least 0.2 mol equivalen-ts of the basic amino radicals of an alkanolamine of the general formula wherein R is hydrogen, and alkyl radical of 1 to 4 carbon atoms, a hydroxyalkyl radical having 2 to 4 carbon atoms, or one of the radicals CH CH -NR"R"', and CI-I CH -CH NR"R"; R" is a hydroxyalkyl radical having 2 to 4 carbon atoms; and R' is hydrogen, or a hydroxyalkyl radical having 2 to 4 carbon atoms.

The monocarboxylic lower alkanoic acids in which the precondensates of the invention are soluble include formic acid and acetic acid.

The water insoluble precondensates which are soluble in dilute aqueous lower monocarboxylic alkanoic acids may be prepared according to various methods.

They are obtained by heating 1 mol of an aminotriazine, and particularly of melamine, with 1 to 2 mols of an aliphatic monocarboxylic acid having more than carbon atoms and particularly 15 to 19 carbon atoms; 16 to 18 mols, and particularly 9 to 15 mols of paraformalde- 4 hyde; and 0.2 to 1.2 mols, and preferably 0.5 to 1.0 mol of an alkanolamine which preferably is of the formula RAH.

wherein R is hydrogen or a hydroxyalkyl radical having 2 to 3 carbon atoms; and R is a hydroxyalkyl radical having 2 to 3 carbon atoms; in the presence of a monohydric alkanol having 1 to 5 carbon atoms to a temperature of to 140 C. while volatile constituents are permitted to distill from the reaction mixture until the residue is soluble in a dilute monocarboxylic acid, more particularly in hot, 5 to 10% acetic acid.

The aliphatic monocarboxylic acid having more than 10 carbon atoms may be replaced in the above synthesis method by 0.5 to 1 mol of the corresponding acid anhydride.

Precondensates of the same type are arrived at when the aminotriazine and the aliphatic monocarboxylic acid having more than 10 carbon atoms or its anhydride are replaced by 1 mol of a melamine derivative in which 1 to 3 hydrogen atoms of the amino radicals are replaced by aliphatic acyl radicals having more than 10 carbon atoms and particularly 15 to 19 carbon atoms.

Yet another method of preparing the precondensates of the invention employs as starting materials methylolaminotriazines, and particularly methylol melamines which are etherified with lower monohydri-c alkanols having 1 to 4 carbon atoms. 1 mol of the etherified methylol melamine is heated with 1 to 2 mols of an aliphatic monocarboxylic acid having more than 10 carbon atoms, and preferably 15 to 19 carbon atoms to a temperature of 200 C., and preferably until almost the entire amount of fatty acid is present in the combined forms. This reaction may be performed at ambient pressure or in a vacuum. The intermediate product obtained is then reacted with 0.2 to 1.2 mols, preferably 0.5 to 1.0 mol of an alkanolamine which preferably has the formula wherein R and R are the radicals mentioned above, by heating to a temperature of 100-130 C. until a sample of the condensation product is soluble in a dilute, aqueous monocarboxylic acid such as formic acid or acetic acid. The last mentioned condensation reaction also may be performed in a vacuum.

According to yet another method, one mol of a 2,4- diamino-6-alkyl-1,3,5-triazine, the alkyl group is containing at least 10, preferably 15 to 22 carbon atoms, is heated with paraformaldehyde preferably in amounts of 5 to 8 mols, with 0.2 to 1.2 mols, and preferably with 0.4 to 1.0 mol of an alkanolamine which is preferably of the formula wherein R and R have the same meaning, and with a lower monohydric alkanol having one to five carbon atoms. The volatile constituents are permitted to distil from the reaction mixture, and heating is continued until the product is soluble in a dilute monocarboxylic acid, andi particularly in hot five to ten percent aqueous acetic ac1 A further method of synthesizing the pre-condensates of the invention starts with an aminotriazine derivative which is obtained by reacting one mol of a compound of the formula wherein E is hydrogen, amino radical, alkyl radical with 1 to 22 carbon atoms; with at least 1 mol of an alkyl isocyanate per mol of said aminotriazine derivative and at most one mol of said alkyl isocyanate per equivalent amino radicals. Especially used are derivatives obtained by heating one mol of melamine with 1.2 to 2 mols of said alkylisocyanate.

The alkyl radical of said alkyl isocyanate has more than ten, and preferably fifteen to nineteen carbon atoms.

The reaction is performed at 200 to 260 C. until a clear liquid is obtained.

One miol of this intermediate aminotriazine .derivative obtained is heated to 130 to 160 C. with six to eighteen (preferably nine to fifteen) mols paraformaldehyde, 0.2 to 2.0 (preferably 0.7 to 1.5) mols of an alkanolamine, preferably of the formula R N--1 wherein R and R have the same meaning, and a lower ,monohydric alkanol having at most five carbon atoms and preferably four carbon atoms. The volatile constituents are permitted to evaporate from the solution, and heating is continued until the product is .soluble in dilute monocarboxylic acids, such as hot five to ten percent aqueous acetic acid.

It will be understood that the nature of the mono- .c arboxylic acid employed in the solubility test is not critical, and that a5 to acetic acid solution is employedbecause of its convenience and ready availability.

- beobtained with amounts of the acid soluble precondensate which are as low as 0.2% of the alkyl-alkylene .urea employed. The acid soluble precondensates are preferably added to the treating baths as a 50% mixture with an organic solvent which is non-miscible with Water, and particularly with a hydrocarbon or a halogenated hydrocarbon, 'or in the form of the 50% mixture with a material which itself imparts water repellent properties to the fabric, such as paraffin, a wax, or mixtures of both.

The water insoluble precondensates which are soluble in dilute organic acids have an emulsifying effect on the other constituents of the treating baths. Upon drying, and particularly at the temperature of the conventional curing treatment, they become insoluble and water repellent. The precondensates are employed in the form of aqueous emulsions which are prepared by dissolving mixtures of the precondensates with paraffin, wax or solvents in the presence of dilute organic acids. It is also possible to premix dispersions ofthe N-alkyl-N,N'-alkylene ureas with a 50% solution of a precondensate in a solvent which is not miscible with water and free of hydroxyl groups, and to add the premixed dispersions to the treating bath.

When this procedure is followed, the treating bath is prepared by the addition of only one material instead of 2 materials, and only one weighing or measuring operation is involved. Only one concentrated dispersion needs to be diluted in the treating plant. The addition of the precondensate to the alkyl-alkylene urea dispersion also enhances the stability of the latter as more fully disclosed in our Patent No. 3,148,164.

The term textiles and other fibrous materials as used herein will be understood to cover all types of fibrous materials, whether natural or man-made, and all forms which such fabric may assume, such as woven or knitted fabrics, non-woven fabrics such as felts, sheet material fabrics.

traces of staining material can usually only be removed by saturating the material with a suitable solvent which after evaporation leaves annular areas of discoloration. Water absorption as reported in the examples which .will now follow is measured on the Bundesmann spray apparatus. .The rating excellent water repellency is applied to fibrous material which after ten minutes testing on the spray apparatus does not show any sign of wetting. Good water repellency is a rating given .to materials showing first traces of wetting after ten minutes. No water repellency is reported where the fibrous material is wetted after 10 minutes testing.

Oil repellency is reported as tested by the well known method of Minnesota Mining and Manufacturing Co. The fibrous material is positioned to provide a horizontal surface, and drops of mixtures of purified mineral oil Nujol.) and n-heptane areplaced on the surface. The

mixture containing the highest percentage of n-heptane which does not wet the fabric or the fibrous material under the drop determines the rating. The mixtures of paraffin and heptane are assigned arbitrary rating numbers of 0 to according to the following table:

TABLE 1 Percent n-heptane in mixture (by volume):

Oil repellency rating The following examples are further illustrative of the method of the invention, andit will be understood that the invention is not limited thereto. All parts and percentages are by weight unless otherwise specifically stated. All temperatures are in degrees C.

Example 1 Several lengths of a polyester fabric weighing 50 grams per square meter, having a linen weave of 47 warp thread per centimeter and 40 filling threads per centimeter (both Nm. 200), are respectively saturated with the treating baths described below, extracted between squeeze rolls to a pick-up of 50%, dried at and cured 5 minutes at Bath A.The bath is prepared by stirring 10 grams of the emulsion of an alkyl-alkylene urea prepared as described hereinafter in small consecutive portions into a five-fold amount of water, and by adding the dispersion formed to a mixture of 30 ml. of isobutanol and 700 ml. water whereupon 25 grams of a 30% aqueous dispersion of a polymer are carefully stirred into the mixture. The polymer is obtained by polymerizing a compound of the formula CgFnSOgN The liquid obtained is diluted with cold water to one liter.

Bath B.25 grams of the above described polymer dispersion are added to a mixture of 30 ml. isobutanol and 700 ml. water, and the liquid obtained is diluted with water to one liter.

The oil and water repellency of fabric samples treated in baths A and B is determined immediately after completion of the finishing treatment, and again after 3 laundry cycles in which a fatty alcohol sulfonate is employed as a detergent at a temperature of 40. The results obtained are shown in Table 2.

bonate are added, and the dispersion formed is homogenized by means of a high speed stirrer.

3 grams of the dispersion obtained are stirred in small portions into the five-fold amount of water. The diluted emulsion is then added to a mixture of 20 cc. isobutanol, 20 cc. isopropanol, and 700 cc. water. In this mixture,

TABLE 2 Oil Repcllency Water Absorption, Water Repcllency percent Bath A B A B A B Initial 100++ 100+ 2.5 18 Excellent None. AfterSlaundry eyclesm" 100+ 80 14 25 Good None.

The above mentioned dispersion of the N-alkyl-N,N'- 30 parts of an aqueous 30% dispersions of a copolym'er of alkylene urea is prepared according to the following 80 mol percent ofamonomer of the formula method:

28.5 grams ethylene imine are diluted with 125 grams 2O C F SO N(C H )CH CH OOCCH=CH distilled water, and mixed at 20 with a solution coni i f 12 5 grams distilled Water, 15 grams f and of mol percent butadiene is dispersed by stirring. aqueous ammonia 090 d 45 grams f glycerol The woolen fabric treated with the solution prepared triricinoleate which has been etherified with 30 mols of described above has excellent Water P CY after ethylene oxide. 200 grams octadecyl isocyanate are slowthe treatment, and this Water repellency isprsstisallyun- 1 dd d d b d to h l i b i d i h i altered after three laundry cycles. After three cycles of ring and cooling. After the reaction has gone to complecommercial y Cleaning it is l'edused y to a rating of tion, 450 grams distilled water and 10 grams aqueous g The Oil repellency has all initial rating of ammonia solution are added, and the mixture is mechanand is reduced after three launderings as Well as after ically homogenized by means of high speed stirrer. It three Cycles of y cleaning to a rating of i is diluted to 1,000 grams by means of a solution of 66 A further impfovelhfiht can be achieved by adding to grams octadecyl oxymethylene-hydroxyethylmorpholinithe bath prior to the addition of the polymer dispersions um chloride in 134 grams distilled water. 0.1 to 50 cc. of an acidified aqueous dispersion containing about 10 percent of one of the products described herein- Example 2 after. This addition improves the processing character- A cotton popeline weighing 160 grams per squar meter istics of the bath as far as freedom from formation of and having 58 Warp threads (Nm. 77) per centimeter and coatings on the Padding T0115 is Concfirned, and 3180 24 filling threads (Nm. 65) per centimeter, is treated in Proves the initial oil and Water p y, as i as the the manner d ib d in Example 1 with a b th hi h resistance of the finish to laundering and dry cleaning. contains 10 grams of the afore-described alkyl-alkylene r condensate (a).90 parts stearic acid are melted in urea dispersion, 25 grams of the afore-described emulsion a three-neck flask equipped with a condenser, a stirrer, of the polymerisate having perfluoroalkyl radicals, and and a thermometer. 148 parts of methanol, 75 parts of additionally 15 grams of 100% dimethylol urea and 4 paraformaldehyde, and 25 parts of melamine are added grams ammonium chloride per liter. to the molten acid with continuous stirring while a tem- The bath is prepared by first dissolving the dimethylol perature of approximately 60 is maintained. As soon as urea in the ten-fold amount of hot water, permitting the all the ingredients are mixed, the temperature is slowly solution to cool, and adding thereto isobutyl alcohol. increased to 120 within about 2 hours, and within an 7 This mixture is combined with the other ingredients, and additional hour from 120 to 130 while the methanol the ammonium chloride is added last in the form of is permitted to distill off. When as a temperature of a5% aqueous solution. 130 is reached, 25 parts of triethanolamine are added The cotton fabric finished in the bath described above whereby the temperature is reduced to about 115. This has an initial water absorption of 18.1%, good water temperature is maintained while the mixture is being repellency, and an oil repellency rating of 90. After the stirred. As soon as a sample is clearly soluble in hot, fabric is laundered three times at 60, the water absorpaqueous, 6% acetic acid, 190 parts of trichloroethylene tion and the oil repellency are not significantly affected. are stirred in, and the clear solution obtained is permitted The recovery angle of the finished material is vto cool. When 10 to 15% of acetic acid are added thereefflge 0f p-W and filling-Wise test) as mpared to to in the form of a strong aqueous solution, and the rea W Y angle of 0f the uhfinishad fahficsultant mixture is diluted with water, a stable emulsion Example 3 having small dispersed particles is obtained. If this dis- 60 persion is to be prepared in large amounts it is preferably Samples of wool gabardine weighing 300 grams per made up with the aid of a mechanical high speed stirrer. ."square meter and having a twill weave with 27 warp Triethanolamine may be replaced in the above r'eacthreads per centimeter (Nm. 19) and 20 filling threads tions by tripropanolamine. per centimeter (Nm. 22) are respectively saturated with Precondensate (b).182 parts of methanol, 35 parts the finishing bath described below, extracted to a pickof triethanolamine, parts of paraformaldehyde, and up of approximately 65%, dried at and cured 5 190 parts of atechnical grade of 1,3-diamino-5-hexadecy1- minutes at 2,4,6-triazine containing 80% of the pure compound while An alkyl-alkylene urea dispersion is prepared as folthe remainder consists essentially of fatty acid nitriles lows: having an average molecular weight of about 255, are A mixture of 250 parts water, 3 parts potassium car- 70 mixed in a three-neck flask equipped as described above, bonate, 40 parts stearyl alcohol polyglycol ether (20 mols and heated to a temperature of -145 within about ethylene oxide per mol stearyl alcohol) and 28.5 parts 2 to 3 hours while the alcohol is permitted to distill oif. ethylene imine is gradually added drop by drop to 200 The maximum temperature is maintained until a sample parts heptadecyl isocyanate. When the reaction is comof the product in the flask is completely and clearly pleted 450 parts-water containing 2 parts potassium car- 75 soluble in hot, 6% acetic acid. The main body of the reaction mixture is then cooled to about 90, and 260 parts of trichloroethylene are added. A light yellow solution is obtained which is readily emulsified in Water in the presence of 15 to 30% of acetic acid. The emulsion is very stable.

Precondensate (c).525 parts of isobutanol are mixed in a three-neck flask fitted with a stirrer, a reflux condenser, and a thermometer, with 35 parts diethanolamine, 90 parts of paraformaldehyde, and 150 parts of a product obtained by jointly heating 1 mol of melamine with 2 mols of heptadecyl isocyanate to about 240 C. The mixture obtained is refluxed for 3 hours whereupon the reflux condenser is replaced by a descending condenser, and the alcohol is distilled off over a period of 2 to 3 hours while the temperature is increased to 150155 C. This temperature is maintained until the product is soluble in hot, 6% acetic acid. It is then cooled to about 110 and mixed with 240 parts of toluene. An almost transparent, light brown solution is obtained which in the presence of 12 to 28% acetic acid forms a good, stable dispersion in water.

Instead of the approximately 50% solutions of the precondensates of the invention with organic solvents, mixtures of the precondensates with about equal amounts of paraflin may be made, and these mixtures may be added to the treating bath instead of the solvent solution. If such paraifin mixtures are employed, it is necessary to fuse the waxy mixtures at temperatures of approximately 60-80 before they are stirred with approximately 'equal to three-fold amounts of 30% aqueous, acetic acid having a temperature of about 80. The mixtures obtained may be diluted gradually with hot water, and finally chilled with 3 to volumes of cold water whereupon they are ready to be added to the treating bath.

When di-i-propanolamine is employed in the condensation reaction to replace an equimolecular amount of the diethanolamine, closely similar results are obtained.

Example 4 A nylon fabric similar in weave and weight to the polyester fabric described in Example 1 is saturated with the bath described below, extracted to a pick-up of about 60%, dried at 1210", and cured for 5 minutes at 130.

One of the finishing agents in the bath is an alkylalkylene urea prepared as follows:

A mixture of 250 parts water, 15 parts of aqueous concentrated ammonia solution (d. 0.90), 45 parts of triricinolein polyglycol ether (30 mols ethylene oxide per mol triricinolein), and 28.5 parts ethylene imine are slowly added, drop by drop to 200 parts heptadecyl isocyanate with strong agitation. After the reaction is completed, 450 parts of water containing parts aqueous ammonia solution are added, and the dispersion formed is homogenized by means of a high speed stirrer. It is diluted with a solution of 66 parts of hexadecylhydroxymethylene-pyridinium chloride in 134 parts of water, and mixed by stirring with 25 parts of the solution of a water insoluble precondensate soluble in organic acids prepared as described below:

370 parts methanol, 69 parts triethanolamine, 187 parts paraformaldehyde, and 63 parts melamine are mixed in a three-neck flask equipped with a descending condenser, a stirrer, and a thermometer. While the mixture is continuously stirred, its temperature is slowly raised. When it reaches 40, 225 parts of a technical grade of stearic anhydride (acid number approximately 3 to 7) are added, and the temperature is gradually raised within about 2 to 3 hours to about 120 while the alcohol is permitted to distill off. The mixture is held at this temperature until the product formed is soluble in hot, 6% acetic acid. 475 parts of a mixture of one part of volume of tetrachlorethylene and 3 parts of volume of benzene are added.

Various modifications are contemplated, and may be obviously resorted to by those skilled in the art without departing from the spirit and scope of the invention as hereinafter defined by the appended claims, as only preferred embodiments have been disclosed.

What we claim is:

1. A method of treating textile materials and other fibrous materials which comprises impregnating said material with an aqueous treating bath containing a first organic compound having a plurality of perfluoroalkyl radicals, each of said radicals having at least four carbon atoms; and a second organic compound which is an N- alkyl-N, N-alkylene urea, the alkyl radical of said second compound having more than ten carbon atoms, and the alkylene radical of said second compound having two to three carbon atoms; drying the impregnated material; and curing the dried material, wherein said bath further contains a water insoluble third organic compound soluble in dilute aqueous solutions of monocarboxylic lower alkanoic acids, said third compound being a precondensate of an aminotriazine having at least two amino radicals directly bound to the triazine ring, said ring being free of directly bound hydroxyl radicals, with formaldehyde and a monohydric lower alkanol, said precondensate having for each triazine ring at least one alkyl radical of more than ten carbon atoms and at least 0.2 mol equivalent of the basic amino group of .an alkanolamine of the formula wherein R is a member selected from the group consisting of hydrogen, an alkyl radical having one to four carbon atoms, a hydroxyalkyl radical having two to four carbon atoms, and the radicals --CI-I CH -NRR" and -CH CH CH NR"R"'; R" is a hydroxyalkyl radical having two to four carbon atoms; and R is selected from the group consisting of hydrogen and a hydroxyalkyl radical having two to four carbon atoms.

2. A method according to claim 1, wherein said bath contains between substantially 2 and 15 grams per liter of said first compound, said first compound being a polymer essentially consisting of monomer units, at least one half of said units having a perfluoroalkyl radical of at least four carbon atoms, and wherein said bath contains between one and fifteen grams per liter of said second compound, said alkyl radical of said second compound having between fifteen and nineteen carbon atoms, and said alkylene radical thereof having two carbon atoms; and wherein said bath contains 0.002 to 10 grams per liter of said third organic compound.

3. A method according to claim 2, wherein said third compound is used in form of a mixture with an about equal amount of a water insoluble organic substance selected from the group consisting of hydrocarbons and waxes.

4. A method according to claim 2, wherein said alkanolamine is a dialkanolamine having two to three carbon atoms in each hydroxyalkyl radical.

5. A method according to claim 2, wherein said alkanolamine is a trialkanolamine having two to three carbon atoms in each hydroxyalkyl radical.

6. A textile material treated according to claim 1.

References Cited by the Examiner UNITED STATES PATENTS 2,314,968 3/1943 Bestian et al. 117139 XR 2,642,416 6/1953 Ahlbrecht et al 117-436 2,864,781 12/1958 Albrecht et al. 117-1395 XR 3,034,925 5/1962 De Marco et al.

WILLIAM D. MARTIN, Primary Examiner.

RICHARD D. NEVIUS, Examiner. 

1. A METHOD OF TREATING TEXTILE MATERIALS AND OTHER FIBROUS MATERIALS WHICH COMPRISES IMPREGNATING SAID MATERIAL WITH AN AQUEOUS TREATING BATH CONTAINING A FIRST ORGANIC COMPOUND HAVING A PLURALITY OF PERFLUOROALKYL RADICALS, EACH OF SAID RADICALS HAVING AT LEAST FOUR CARBON ATOMS; AND A SECOND ORGANIC COMPOUND WHICH IS A NALKYL-N'',N''-ALKYLENE UREA, THE ALKYL RADICAL OF SAID SECOND COMPOUND HAVING MORE THAN TEN CARBON ATOMS, AND THE ALKYLENE RADICAL OF SAID SECOND COMPOUND HAVING TWO TO THREE CARBON ATOMS; DRYING THE IMPREGNATED MATERIAL; AND CURING THE DRIED MATERIAL, WHEREIN SAID BATH FURTHER CONTAINS A WATER INSOLUBLE THIRD ORGANIC COMPOUND SOLUBLE IN DILUTE AQUEOUS SOLUTIONS OF MONOCARBOXYLIC LOWER ALKANOIC ACIDS, SAID THIRD COMPOUND BEING A PRECONDENSATE OF AN AMINOTRIAZINE HAVING AT LEAST TWO AMINO RADICALS DIRECTLY BOUND TO THE TRIAZINE RING, SAID RING BEING FREE OF DIRECTLY BOUND HYDROXYL RADICALS, WITH FORMALDEHYDE AND A MONOHYDRIC LOWER ALKANOL, SAID PRECONDENSATE HAVING FOR EACH TRIAZINE RING AT LEAST ONE ALKYL RADICAL OF MORE THAN TEN CARBON ATOMS AND AT LEAST 0.2 MOL EQUIVALENT OF THE BASIC AMINO GROUP OF AN ALKANOLAMINE OF THE FORMULA 